CN1727320A - reactive benzophenone photoinitiator and preparation method thereof - Google Patents
reactive benzophenone photoinitiator and preparation method thereof Download PDFInfo
- Publication number
- CN1727320A CN1727320A CN 200510037763 CN200510037763A CN1727320A CN 1727320 A CN1727320 A CN 1727320A CN 200510037763 CN200510037763 CN 200510037763 CN 200510037763 A CN200510037763 A CN 200510037763A CN 1727320 A CN1727320 A CN 1727320A
- Authority
- CN
- China
- Prior art keywords
- benzophenone
- compound
- oxygen base
- propoxy
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 title claims description 99
- 239000012965 benzophenone Substances 0.000 title claims description 97
- 238000002360 preparation method Methods 0.000 title abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 75
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 49
- 229910052760 oxygen Inorganic materials 0.000 claims description 49
- 239000001301 oxygen Substances 0.000 claims description 49
- 238000000016 photochemical curing Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 10
- CUUQFOTXVOJTMC-UHFFFAOYSA-N OC(C(=O)[O])=CC Chemical compound OC(C(=O)[O])=CC CUUQFOTXVOJTMC-UHFFFAOYSA-N 0.000 claims description 7
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 239000012736 aqueous medium Substances 0.000 claims 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 claims 1
- 239000002609 medium Substances 0.000 claims 1
- -1 Hydrogen Chemical class 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 17
- 238000004383 yellowing Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- 229940125782 compound 2 Drugs 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- VZTQQYMRXDUHDO-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-(2-hydroxy-3-prop-2-enoyloxypropoxy)phenyl]propan-2-yl]phenoxy]propyl] prop-2-enoate Chemical compound C=1C=C(OCC(O)COC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OCC(O)COC(=O)C=C)C=C1 VZTQQYMRXDUHDO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 229960004418 trolamine Drugs 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical class C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 101100132433 Arabidopsis thaliana VIII-1 gene Proteins 0.000 description 2
- 101100459319 Arabidopsis thaliana VIII-2 gene Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- VUOBJKAYKZZORE-UHFFFAOYSA-N [2-(2-hydroxyethyl)phenyl]-phenylmethanone Chemical compound OCCC1=CC=CC=C1C(=O)C1=CC=CC=C1 VUOBJKAYKZZORE-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
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- 229940126214 compound 3 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 description 1
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
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- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 description 1
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 1
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 1
- YPCHGLDQZXOZFW-UHFFFAOYSA-N [2-[[4-methyl-3-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]carbonylamino]phenyl]carbamoyloxymethyl]-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound CC1=CC=C(NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C)C=C1NC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C YPCHGLDQZXOZFW-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- YXUPZGKORWTXID-UHFFFAOYSA-N domiphen Chemical compound CCCCCCCCCCCC[N+](C)(C)CCOC1=CC=CC=C1 YXUPZGKORWTXID-UHFFFAOYSA-N 0.000 description 1
- 229960000629 domiphen Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 208000030454 monosomy Diseases 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012713 reactive precursor Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a compound of a general formula I and a preparation method thereof. Wherein Z1Hydrogen, Z; z is a substituent structure of general formulas II, III and IV; wherein R is1，R2Independently of hydrogen, C1－6Alkyl radical, C1－6An alkoxy group; r3Is hydrogen, methyl; n is 1, 2, 3. The compound with the structure shown in the general formula I can be used as a photoinitiator in an ultraviolet curing system, has the effects of reducing odor and yellowing generated in the using process and shows remarkable high efficiency.
Description
Technical field: the reaction type photoinitiator of benzophenone that the present invention relates to have active carbon-carbon double bond.Its preparation method is the benzophenone derivates and the Racemic glycidol compound reaction that has active carbon-carbon double bond by the band phenolic hydroxyl group, or is made with (methyl) vinylformic acid (ester) reaction by the benzophenone derivates of band phenolic hydroxyl group.Benzophenone cpd provided by the invention can be used as light trigger in the ultraviolet curing system, have high-efficient characteristic, has to reduce the effect that produces stink and yellowing in the use.
Background technology: the smooth realization of UV curing technology and industry are promoted to a great extent with the selection of light trigger and are used relevant.As everyone knows, benzophenone be a kind of inexpensive, be widely used, a photoinitiator that usage quantity is big, can cause offensive odour but its inherent shortcoming is that molecular weight is low, produce fragment after its photolysis, after another great defective is to be the coating curing of light trigger with the benzophenone, tanned by the sun the obvious probably xanthochromia of coating in the sun several days.Because above-mentioned defect factors, make its Application Areas be restricted, particularly aspect the wrapping material of Food Contact.For a long time, people also always be devoted to seek the smell that reduces in the benzophenone use and the approach of yellowing.
At the sublimability of benzophenone, by the structure of benzophenone is carried out the modification of long-chainization, so, reduced its volatility, also increased its perviousness simultaneously at coatingsurface.In fact, a lot of derivatives of benzophenone all are effective hydrogen-capture-type light initiators, comprising Michler's keton, 4, the structure that 4 '-two phenoxy group benzophenone and other aminoalkyl replace, but because the limitation on its structural performance, the problem of smell and yellowing is not effectively overcome.
The present invention relates to the novel diphenyl ketone photo initiator of a class, it not only has good photopolymerization activity, and extinction usefulness strengthens greatly, and simultaneously because active carbon-carbon double bond can participate in copolyreaction, it has remarkable improvement aspect stink and the yellowing overcoming.
Summary of the invention: in order to solve the smell at benzophenone structural, the defective of yellowing, realize that simultaneously it has the active requirement of good photopolymerization, the invention discloses a kind of benzophenone derivates that has active carbon-carbon double bond and can be used as novel photoinitiator with general formula (I), and preparation method about this general formula (I) is provided, have the advantage that reaction conditions is easy, product purity is high.
Wherein: Z
1=hydrogen, Z; Z is the substituent structure of general formula I I, III, IV.
R wherein
1, R
2Independently be hydrogen, C
1-6Alkyl, C
1-6Alkoxyl group; R
3Be hydrogen, methyl; N=1,2,3.
This general formula I structural compounds can be applicable to many light initiation systems very effectively, as the light trigger in the ultraviolet curing system, has and reduces the effect that produces stink and yellowing in the use, and present remarkable high efficiency.
Owing on the unitary phenyl ring of benzophenone structural the specified substituent Z that contains active carbon-carbon double bond has been arranged
1And Z, the light trigger that the present invention relates to will have confessedly response type characteristic, and can have 4,4 ' of benzophenone-disubstituted characteristic.So this general formula I structural compounds has good response characteristic, after photodissociation, can not produce the fragment small molecules of free property, also just avoided the generation of stink naturally.Simultaneously, because its each unsaturated compound to the ultraviolet photo-curing system has the copolymerization effect, so its pairing light solidifying coating also just can effectively overcome yellowing.
The present invention relates to new compound with general formula I.
The present invention relates to and utilize the general formula I benzophenone derivates to be applied to the photopolymerization reaction of the unsaturated compound of thiazolinyl structure, or contain the system of the unsaturated compound of thiazolinyl structure as light trigger.
The present invention relates to the additive that the ultraviolet photo-curing system contains at least a ethylenic unsaturation based compound and other form, the compound that contains a kind of general formula I in this system at least is as light trigger.
In addition, the invention still further relates to band and carry out the photocuring embodiment of photocuring polymerization system and the preparation of photocureable polymer as light trigger with compound of Formula I.
Consider the response type base group modification of benzophenone reactive precursor structure.In general formula I, Z can be a general formula I I building stone.Under first kind of situation, the molecular formula of the benzophenone derivates that it is corresponding is shown in general formula I a.
Wherein:
In above-mentioned general formula I a structure, R
1, R
2, R
3Definition same as above.Formula Ia corresponds to the benzophenone derivates of the acrylate end groups structure of branched hydroxy groupization.
In general formula I, Z can be the general formula III building stone.Under second kind of situation, the molecular formula of the benzophenone derivates that it is corresponding is shown in general formula I b.
In above-mentioned general formula I b structure, R
1, R
2Definition same as above.Formula Ib corresponds to the benzophenone derivates of allyl end group branched hydroxy group structure.
In general formula I, Z can be a general formula I V building stone.Under the third situation, the molecular formula of the benzophenone derivates that it is corresponding is shown in general formula I c.
Wherein:
In above-mentioned general formula I c structure, R
1, R
2Definition same as above.Formula Ic corresponds to the benzophenone derivates of acrylate structural end-group structure.
General formula I a and Ib compound are owing to exist the hydroxyl structure of collateralization, and it has water-wet behavior preferably.The present invention relates to the target compound of general formula I a and Ib structural performance, it is particularly useful for aqueous phase system and prepares aqueous systems polymers soln or polymer dispersed system, or based on the radiation-curable couting of aqueous polymerization thing dispersion liquid.
In addition, the invention still further relates to general formula I a and Ib compound and carry out the photocuring embodiment of water-soluble polymkeric substance and aqueous dispersion polymers and the preparation of water-soluble or hydrophilic polymer as the light trigger of ultraviolet photo-curing system.
In the general formula I structure, work as Z
1During=H, compound of Formula I is one-sided active carbon-carbon double bond substituted benzophenone structure; Work as Z
1During=Z, compound of Formula I is to have 4,4 ' on the phenyl ring unit of benzophenone-response type characteristic that symmetrical active carbon-carbon double bond replaces.
The description of comprehensive above-mentioned mutual-through type I, Ia, Ib, Ic structure replaces structure in conjunction with general formula I I, III, IV, considers and the variable situation of structurally associated that preferred compound of formula I of the present invention comprises as follows.
4-(2-hydroxyl-3-acryl oxygen base-propoxy-) benzophenone
4-(2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone
4,4 '-two (2-hydroxyl-3-acryl oxygen base-propoxy-) benzophenone
4,4 '-two (2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone
4-(2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone
4,4 '-two (2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone
4-(2-acryl oxygen base-ethyl) benzophenone
4-(2-methacryloyl oxygen base-ethyl) benzophenone
4,4 '-two (2-acryl oxygen base-ethyl) benzophenone
4,4 '-two (2-methacryloyl oxygen base-ethyl) benzophenone
The preparation of compound of Formula I can be adopted the common method of organic synthesis.Can utilize the benzophenone derivates and the Racemic glycidol compound reaction that has active carbon-carbon double bond of band phenolic hydroxyl group, or make with (methyl) acrylate reactions by the benzophenone derivates of band phenolic hydroxyl group.
Concrete preparation scheme comprises three links:
1) general formula I a compound can be by the general formula V-1 and the V-2 benzophenone cpd of hydroxyl replacement
(methyl) glycidyl acrylate compounds with general formula VI structure
Carry out condensation reaction and obtain.
Among above-mentioned formula V-1, V-2, the VI, R
1, R
2, R
3Definition with the definition in the general formula I.
2) in the preparation scheme of general formula I b compound, can be by the glycidyl allyl ether compounds of above-mentioned general formula V-1 and V-2 compound and general formula VII structure
Carry out condensation reaction and obtain.
Among above-mentioned formula V-1, V-2, the VII, R
1, R
2, R
3Definition with the definition in the general formula I.
3) general formula I c compound can be by general formula VIII-1 and the VIII-2 benzophenone cpd that has hydroxyl structure
(methyl) acrylic ester compound with general formula I X structure
Carry out esterification and obtain.
Among above-mentioned formula VIII-1, VIII-2, the IX, R
1, R
2, R
3, the definition of n is with the definition in the general formula I, R
4Be hydrogen, methyl, ethyl.The present invention relates at this provides above-mentioned several preparation method about preparation general formula I structure benzophenone derivates.At different structure type Ia, Ib, Ic, three kinds of process programs are provided among the present invention respectively.
In the preparation of general formula I a and Ib compound, the general use than theoretical amount Duo 10～20% the active carbon-carbon double bond Racemic glycidol of band compound to guarantee the reacting completely transformation efficiency that corresponding raising is reacted.When preparation Ia and Ib compound, reaction is carried out in the presence of basic catalyst.Basic catalyst commonly used comprises alkali metal hydroxide and carbonate, as sodium hydroxide, potassium hydroxide, yellow soda ash etc.Exist in the condensation reaction tetramethyl-ammonium halide compound to reaction carry out favourablely, comprise tetramethyl ammonium chloride, Tetramethylammonium iodide etc., be good wherein with tetramethyl ammonium chloride, it has the effect that suppresses epoxide open loop autohemagglutination.These catalyst consumption are 0.1～10% of Racemic glycidol compound, wherein are advisable with 1～5%.
When carrying out above-mentioned preparation feedback, normally under condition of stirring, benzophenone derivates is added in Racemic glycidol compound and the mixture of catalysts, other feed way too can.Reaction can be carried out in the inert polar solvent, and common solvent comprises acetone, methylethylketone, THF, DMF, DMSO, N-BUTYL ACETATE etc.
Above-mentioned preparation feedback carries out under 60～120 ℃ usually, generally is advisable with 80～90 ℃.The soaking time of reaction process generally need be at 2 hours～24 hours transformation efficiencys to guarantee to react, and suitable soaking time is 6～8 hours.Usually, improve temperature of reaction and help accelerated reaction, but also unsuitable too high, to avoid causing polymerism.
In the preparation scheme of general formula I a and Ib compound, the yield of entire reaction is between 80～95%.Generally after condensation reaction finishes, carry out the solvent steaming and remove, resulting thickness oily product can be directly used in the ultraviolet photo-curing system as the light trigger with response characteristic without purification process.Purifying if desired can adopt the mode of post drip washing.
In the preparation scheme of Ic general formula compound, the invention provides alcoholic acid esterification reaction and two kinds of technical schemes of transesterification reaction.In the alcoholic acid esterification scheme, be solvent generally with benzene, toluene, hexanaphthene, heptane.Use acidic substance effect esterifying catalyst,, be preferably the first two kind as p-methyl benzenesulfonic acid, trifluoromethane sulfonic acid, the vitriol oil and strong-acid ion exchange resin.In transesterification reaction, catalyzer such as purity titanium tetraethoxide commonly used, four titanium butoxide, temperature of reaction is preferably 90～110 ℃ at 70～120 ℃.In order to guarantee that successful reaction carries out, need be separated timely as water, methyl alcohol, the ethanol of by product, usual means has water-and-oil separator and efficient fractional column.
At the unsaturated photo-curing system of thiazolinyl, compound of Formula I is used as the method for light trigger and follows photocuring system commonly used in the UV curing system, and its implementation method is consistent with light trigger commonly used.
In photocuring system, compound of Formula I is as the addition 0.01～20% (wt.) of light trigger, preferable range 0.1～10% (wt.).Mostly the light trigger product that relates to based on this project is liquid form, or in just can the directly polymerization decorum, stirs behind its simply dissolving.The system that can be aggregated comprises simple function group that free radical causes or polyfunctional group unsaturated monomer, oligomer, prepolymer, or the polymkeric substance of these oligopolymer, performed polymer and unsaturated monomer.Under specific situation, can there be other additive if necessary, as oxidation inhibitor, UV light absorber, dyestuff, pigment, also comprise other known light trigger and accelerator certainly.
The unsaturated compound that is fit to is meant the compound that contains the two keys of active C=C, and two keys herein comprise connection halogen atom, acyl group, cyano group, carboxylicesters, amide group, ether and aryl, also comprises connecting other pair key and three bond structures.Concrete example comprises: vinylchlorid, vinylidene chloride, vinyl cyanide, methacrylonitrile, the acrylic or methacrylic acid esters (comprises methyl, ethyl, normal-butyl, the tertiary butyl, cyclohexyl, the 2-ethylhexyl, benzyl, benzene oxygen ethyl, hydroxyethyl, hydroxypropyl, low-alkoxy ethyl or tetrahydrofuran base), vinyl acetate, propionate, vinyl acrylate or succsinic acid vinyl acetate, the N-vinyl pyrrolidone, the N-vinylcarbazole, vinylbenzene, Vinylstyrene, the mixture of substituted phenylethylene and above-claimed cpd.
Formula of I compound of the present invention solidifies as the UV that light trigger is particularly useful for shallow layer, and for example usual material and the top coat of base material mainly refer to paper, woodenware, fabric, plastics and metal.Oven dry and curing that another important use field is a top coat mainly are marking ink, silk screen printing.Wherein, the latter can well be applicable to can, pipe fitting and Materials for Metal Packaging field.
In the present invention, the benzophenone cpd of general formula I a, Ib structure is because it has suitable water-wet behavior, and it is as the photopolymerization reaction of light trigger applicable to the unsaturated materials of aqueous phase system.Defined herein aqueous phase system be meant the unsaturated monomer substance dissolves or (with) emulsion dispersion is in water.Containing specific polymerization single polymerization monomer in this aqueous phase system, also can be the mixture with the copolymerisable monomer of other type.The unsaturated compound needs that are fit to are dissolved in the water on certain suitable degree, also can be being dispersed in the water of having no problem.At first can be to have high polar vinyl compound of having of characteristic group and acrylic compound, for example can be monocarboxylic acid or the di-carboxylic acid that contains the thiazolinyl structure, concrete as vinylformic acid, methacrylic acid, toxilic acid and fumaric acid and their formed an alkali metal salt and ammonium salt.Again can be as acrylamide, Methacrylamide, maleimide, vinyl cyanide, methacrylonitrile.Also can be the water miscible vinyl compound that contains, for example N-vinyl pyrrolidone and N-vinylcarbazole.The content of above-mentioned these monomeric substances in aqueous phase system can be 10～80% (wt.), preferably 30～70% (wt.).
Simultaneously, the monosomy material in the photocuring system also can contain other copolymerizable unsaturated compound, for example acrylate and methacrylic ester, ethenyl derivatives, and concrete can be vinylchlorid, vinylidene chloride, vinylbenzene and Vinylstyrene.The how unsaturated compounds that perhaps has crosslinking feature is as ethylene acrylate, hexylidene glycol diacrylate, pentaerythritol diacrylate.Simultaneously, can add unsaturated oligomer, performed polymer or polymkeric substance, as acrylated vibrin, Resins, epoxy, urethane resin.In principle, be used as under the situation of ultra-violet curing light trigger at general formula I a and Ib structure, the addition of copolymerizable additive can be advisable to be no more than 20% of overall optical polymeric system less than water-soluble monomer in aqueous phase system.In addition, in above-mentioned aqueous phase system, also can add cosolvent, solubilizing agent and emulsifying agent.As aliphat single-alcohol or how pure, concrete as methyl alcohol, ethanol, Virahol, ethylene glycol, glycerine; Also can be negatively charged ion, positively charged ion, both sexes and nonionogenic tenside, as sulfonation paraffin, alkyl sulfuric ester, fatty acid alkali metal salt, fatty alcohol sulfate, polyoxyethylene glycol or ethoxylated alkyl phenols.The consumption of examples of such additives is according to common using method.
Because general formula I a, Ib compound have than high reaction activity and suitable water-wet behavior, in the water photocuring system, keto-acid Ia and Ib compound are 0.1～10% (wt.) of whole system as the consumption of light trigger, are preferably 0.2～5% (wt.).
In photocuring system if when using light trigger, add suitable accelerator and will help carrying out smoothly of photocuring reaction.As organic amine, phosphine, alcohol, mercaptan etc., in this type of accelerator structural unit 1 contains-and the CH-group links to each other with heteroatoms.Suitable accelerator is primary, aliphatics, aromatic series and the heterocyclic amine compound of secondary, uncle's type.Concrete as, butylamine, dibutylamine, Tributylamine, hexahydroaniline, benzyl dimethyl amine, dicyclohexylamine, trolamine, N methyldiethanol amine, phenyldiethanol-amine, piperidines, piperazine, morpholine, pyridine, quinoline, p-(dimethylamino)-benzoic acid ester, 4,4 '-two dimethylamino benzophenone or 4,4 '-two diethylin benzophenone.Tertiary amine structure preferably is as triethylamine, triisopropylamine, tributylamine, octyl group dimethylamine, domiphen, trolamine, N methyldiethanol amine, N butyl diethanol amine or tripropanolamine.Accelerator described herein is also frequent is expressed as sensitizing agent, coinitiator, and its meaning herewith.
Comprehensive above description, the present invention most preferably is the photopolymerization system that contains trimethylamine.Wherein Ia and Ib structure can be the water photopolymerization systems that contains trimethylamine.
Among the present invention, as light trigger, photocuring reaction can be caused by energy-rich radiation, is preferably ultraviolet ray based on compound of Formula I.The enforcement of photopolymerization reaction can be that successive also can be an intermittence.The time length of illumination is depended on the character and the concentration of the polymerizable thing that adopts, and is also relevant with the character and the consumption of light trigger, and the light intensity with light source also has substantial connection simultaneously.According to what of batch quantity, photocuring time general range can be not wait from several seconds to several minutes.The temperature of photocuring can be selected to be preferably room temperature between 5～100 ℃.The heat that photocuring produces can be removed by method commonly used.
Following example will describe the present invention in detail, but in no case limit the scope of the invention.The preparation that specific examples is mainly concerned with general formula I benzophenone derivates light trigger with and application in the ultraviolet light polymerization system.
Embodiment:
Preparation embodiment one:
The preparation (target compound 1) of 4-(2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone
In the reaction vessel that stirring, thermometer and reflux condensing tube are housed, add glycidyl methacrylate 78g (0.59mol), to dihydroxy benaophenonel 99g (0.51mol), each 0.1g of tetramethyl ammonium chloride 2.5g, hydroquinone of polymerization retarder and hydroquinone monomethyl ether.Under stirring state, reaction mixture is heated to 80 ℃, keep this temperature to continue again to stir 6 hours, behind the cool to room temperature, obtain thickness oily reaction product.Analytical test shows, contain in this oily matter that 1.4% unreacted finishes to dihydroxy benaophenonel.This oily matter can be directly used in the ultraviolet light polymerization system as the response type light trigger.If need, can carry out the post wash-out and handle, obtain the pure product of target compound 1.
By
1HNMR,
13CNMR and MS test illustrate that target product meets the structural performance of 4-(2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C70.61% (70.59%); H5.83% (5.88%).
Preparation embodiment two:
The preparation (target compound 2) of 4,4 '-two (2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone
The preparation of 4,4 '-two (2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone is similar to preparation embodiment one, and initial feed is 4,4 '-dihydroxy benaophenonel.This target compound 2 also is the thickness oily mater.
By
1HNMR,
13CNMR and MS test illustrate that target product meets 4, the structural performance of 4 '-two (2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C65.08% (65.06%); H6.05% (6.02%).
Preparation embodiment three:
The preparation (target compound 3) of 4-(2-hydroxyl-3-acryl oxygen base-propoxy-) benzophenone
The preparation of 4-(2-hydroxyl-3-acryl oxygen base-propoxy-) benzophenone is similar to preparation embodiment one, and initial feed is a glycidyl acrylate.This target compound 3 also is the thickness oily mater.
By
1HNMR,
13CNMR and MS test illustrate that target product meets the structural performance of 4-(2-hydroxyl-3-acryl oxygen base-propoxy-) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C65.01% (69.94%); H5.55% (5.52%).
Preparation embodiment four:
The preparation (target compound 4) of 4-(2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone
In the reaction vessel that stirring, thermometer and reflux condensing tube are housed, add glycidyl allyl ether 64g (0.56mol), to dihydroxy benaophenonel 99g (0.51mol), each 0.1g of tetramethyl ammonium chloride 2.5g, hydroquinone of polymerization retarder and hydroquinone monomethyl ether.Under stirring state, reaction mixture is heated to 80C, keep this temperature to continue again to stir 6 hours, behind the cool to room temperature, obtain thickness oily reaction product.Analytical test shows, contain in this oily matter that 1.2% unreacted finishes to dihydroxy benaophenonel.This oily matter can be directly used in the ultraviolet light polymerization system as the response type light trigger.If need, can carry out the post wash-out and handle, obtain the pure product of target compound 4.
By
1HNMR,
13CNMR and MS test illustrate that target product meets the structural performance of 4-(2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C73.11% (73.08%); H6.43% (6.41%).
Preparation embodiment five:
The preparation (target compound 5) of 4,4 '-two (2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone
The preparation of 4,4 '-two (2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone is similar to preparation embodiment four, and initial feed is 4,4 '-dihydroxy benaophenonel.This target compound 5 is the thickness oily mater.
By
1HNMR,
13CNMR and MS test illustrate that target product meets 4, the structural performance of 4 '-two (2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C67.82% (67.87%); H6.81% (6.79%).
Preparation embodiment six:
The preparation (target compound 6) of 4-(2-acryl oxygen base-ethyl) benzophenone
In the reaction vessel that agitator, thermometer and band water-and-oil separator are housed, add to hydroxyethyl benzophenone 122.1g (0.54mol) vinylformic acid 144g (2.0mol), tosic acid 6g, 200ml toluene, hydroquinone of polymerization retarder monomethyl ether 0.2g successively.Under stirring state, reflux steams the azeotrope of toluene and water, reacts 3 hours globules in the aftercondenser and disappears, and behind the stopped reaction, steams solvent toluene and excessive vinylformic acid, obtains oily matter.With hexanaphthene extraction several times, separate out white solid after the cooling, yield 75%, m.p.:78～80 ℃.
By
1HNMR,
13CNMR and MS test illustrate that target product meets the structural performance of 4-(2-acryl oxygen base-ethyl) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C77.12% (77.14%); H5.75% (5.71%).
Preparation embodiment seven:
The preparation (target compound 7) of 4-(2-methacryloyl oxygen base-ethyl) benzophenone
The preparation of 4-(2-methacryloyl oxygen base-ethyl) benzophenone is similar to preparation embodiment six, and initial feed is for using methacrylic acid instead.This target compound 7 is a white solid, fusing point: 96～98 ℃.
By
1HNMR,
13CNMR and MS test illustrate that target product meets the structural performance of 4-(2-methacryloyl oxygen base-ethyl) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C77.52% (77.55%); H6.15% (6.12%).
Preparation embodiment eight:
The preparation (target compound 7) of 4-(2-methacryloyl oxygen base-ethyl) benzophenone
Agitator, thermometer are being housed and are having in the reaction vessel of fractionation plant, add to hydroxyethyl benzophenone 122.1g (0.54mol) methyl methacrylate 192g (2.0mol), four titanium butoxide 4.5g successively, 200ml toluene, hydroquinone of polymerization retarder monomethyl ether 0.2g.Under stirring state, reflux in time steams methyl alcohol, obtains oily matter.With hexanaphthene extraction several times, separate out white solid after the cooling, yield 81%, m.p.:96～98 ℃.
By
1HNMR,
13CNMR and MS test illustrate that target product meets the structural performance of 4-(2-methacryloyl oxygen base-ethyl) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C77.50% (77.55%); H6.09% (6.12%).
Preparation embodiment nine:
The preparation (target compound 8) of 4,4 '-two (2-acryl oxygen base-ethyl) benzophenone
The preparation of 4,4 '-two (2-acryl oxygen base-ethyl) benzophenone is similar to preparation embodiment six, and initial feed is 4,4 '-dihydroxy ethyl benzophenone.This target compound 8 is a white solid, 63～67 ℃ of fusing points.
By
1HNMR,
13CNMR and MS test illustrate that target product meets 4, the structural performance of 4 '-two (2-acryl oxygen base-ethyl) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C73.06% (73.02%); H5.85% (5.82%).
Preparation embodiment ten:
The preparation (target compound 9) of 4,4 '-two (2-methacryloyl oxygen base-ethyl) benzophenone
The preparation of 4,4 '-two (2-methacryloyl oxygen base-ethyl) benzophenone is similar to preparation embodiment eight, and initial feed is 4,4 '-dihydroxy ethyl benzophenone.This target compound 9 is a white solid, 70～73 ℃ of fusing points.
By
1HNMR,
13CNMR and MS test illustrate that target product meets 4, the structural performance of 4 '-two (2-methacryloyl oxygen base-ethyl) benzophenone.
Concrete ultimate analysis situation is as follows: measured value (calculated value) C73.86% (73.89%); H6.44% (6.40%).
The Application Example part:
Application Example 1: radiation curing nonaqueous phase coating
The situation of photopolymerization each component: 150g oligomerization acrylate epoxy resin Ebecryl 600 (UCB. S.A. (BE) Bruxelles Belgium); 50gHDDA monomer (1; the 6-hexanediyl ester); 5g4,4 '-two (2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone (embodiment two prepared target compound 2) and 3gN-methyldiethanolamine.
With coating apparatus said components is coated on the sheet glass after the skimming treatment (14 * 14cm), coat-thickness 50 μ m.The pocket curing apparatus that above-mentioned coating utilizes Primarc Ltd. to make carries out photocuring.
Condition of cure: high pressure Hg lamp (80watt/cm), belt speed 10m/min, luminous range 10cm.
Under these conditions, obtain completely solidified, be not stained with sticking solidified coating, coating does not have any pungent odour, and solidified coating is by yellow limit property testing, and its yellowing resistance has had remarkable improvement.
Use the same method target compound 2～9 is carried out radiation cure experiments, can obtain identical ideal results.
The experimental result that integrated application is implemented is analyzed, and satisfies Z in the general formula I target compound
1=Z, promptly 4,4, '-symmetric double replaces the target compound of structure, avoiding the characteristic aspect the coating smell especially to have unusual effect as target compound 2,5,8,9.
Application Example 2: radiation curing nonaqueous phase coating
The situation of photopolymerization each component: 65g hangs down acroleic acid polyurethane performed polymer Ebecryl 220 (UCB. S.A. (BE) Bruxelles Belgium); 45gHDDA monomer (1; the 6-hexanediyl ester), 15g pentaerythritol triacrylate and 5g4-(2-methacryloyl oxygen base-ethyl) benzophenone (among the embodiment seven, eight prepared target compound 7) and 3gN-methyldiethanolamine.
Adopt Application Example 1 same method to obtain the coating of thickness 50 μ m,, carry out the photocuring experiment under the situation of belt speed 30m/min at photocuring condition similar application embodiment 1.Obtain completely solidified, do not have and be stained with sticking solidified coating.The smell in coating and the photocuring process and the yellowing resistance of coating significantly improve.
Adopt and use the same method, target compound 1-6,8,9 can obtain same ideal effect.
Application Example 3:UV solidifies marking ink
64g oligomerization acrylate epoxy resin Ebecryl 600 (UCB. S.A. (BE) Bruxelles Belgium), 36gTPGDA monomer (tri (propylene glycol) diacrylate), the mixture of 20g phthalocyanine blue grinds.With 54,4 '-two (2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone (embodiment five prepared target compound 5) and 3gN-methyldiethanolamine.10 fens clock times join in the above-mentioned suspension under stirring state.On enamel paper, be printed as 1 μ m thickness, under the situation of the belt speed of 50m/min, yield of radiation 160watt/cm, be cured then.
Under these conditions, coating obtains completely solidified, and printing paper (sheet) can satisfy the requirement that stacks immediately.Printed matter does not almost have pungent odour.
Adopt and use the same method, target compound 1-4 and 6-9 can obtain same ideal effect.
This embodiment has illustrated that also the maximum absorption wavelength contrast benzophenone BP of the target compound of general formula I has had remarkable increase, can be applied to the photocuring process of coloured system preferably.
Application Example 4: based on the radiation-curable couting of water system
The organic silicon surfactant of the amino co-modified silicone oil type of 20g polyethers is distributed in 170g50% water acrylate epoxy resin Ebecryl 600 (UCB. S.A. (BE) Bruxelles Belgium) emulsion; after the standing over night; add other 170g50% water acrylate epoxy resin emulsion and 40g water; under stirring state, add 5g4-(2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone (embodiment one prepared target compound 1) and 3gN-methyldiethanolamine.
With coating apparatus said components is coated on the sheet glass after the skimming treatment (14 * 14cm), coat-thickness 50 μ m, the sheet glass after the coating was 100 ℃ of dryings 15 minutes.The pocket curing apparatus that above-mentioned coating utilizes Primarc Ltd. to make carries out photocuring.Condition of cure: high pressure Hg lamp (80watt/cm), belt speed 10m/min, luminous range 10cm.
Under these conditions, obtain completely solidified, be not stained with sticking solidified coating.The smell in coating and the photocuring process and the yellowing resistance of coating significantly improve.
Use the same method target compound 2～5 is carried out radiation cure experiments, can obtain identical ideal results; And target compound 6-9 is not owing to existing hydrophilic unit structure, so cannot be applicable to the light solidifying coating of aqueous phase system.
Application Example 5: uv photopolymerization reaction simultaneous test
At first preparation can be carried out photopolymerisable unsaturated polymer system with standby, and its component concentration comprises: 75% oligomerization acrylate epoxy resin Ebecryl 600 (UCB. S.A. (BE) Bruxelles Belgium), 25%HDDA monomer (1,6 hexanediol diacrylate)
With 2.5g light trigger (2.5%wt. is with respect to the polymerizable thing) and 1.5g altogether light trigger (1.5%wt. is with respect to the polymerizable thing) trolamine under stirring state, join in the unsaturated polymerization system of polymerizable of the above-mentioned configuration of 100g and go.
The selection that is used for contrast experiment's light trigger comprises four kinds:
(1.4-2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone (embodiment one prepared target compound 1)
2.4,4 '-two (2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone (embodiment two prepared target compound 2)
(3.4-2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone (embodiment four prepared target compound 4)
4.4,4 '-two (2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone (embodiment five prepared target compound 5)
(5.4-2-acryl oxygen base-ethyl) benzophenone (embodiment six prepared target compound 6)
6.4,4 '-two (2-acryl oxygen base-ethyl) benzophenone (among the embodiment nine prepared target compound 8)
7. benzophenone (the RUNTECURE of Changzhou Huatai Chemistry Co., Ltd. 1020)
8.4-chlorobenzophenone (the RUNTECURE of Changzhou Huatai Chemistry Co., Ltd. 1046)
9.4-benzoyl-4 '-methyl-diphenyl sulfide (the RUNTECURE of Changzhou Huatai Chemistry Co., Ltd. 1030)
Can observe above-mentioned light trigger 1,2,3,4,5,6 owing to have the characteristic of response type, so in the photocuring process and the smell of coating itself almost do not have, and light trigger 7,8,9 in the photocuring process and solidified coating all can produce offending smell.
By coated products is tanned by the sun processing under daylight, observe its xanthochromia, conclusion is the anti-xanthochromia characteristic that light trigger 1,2,3,4,5,6 pairing solidified coatings have remarkable excellence, and utilizes the coated products of light trigger 7,8,9 can produce tangible yellowing behind solar exposure.
Claims (9)
1. benzophenone derivates that has active carbon-carbon double bond is characterized in that it is that general formula is the compound of I:
Wherein: Z
1=hydrogen, Z; Z is the substituent structure of general formula I I, III, IV.
R wherein
1, R
2Independently be hydrogen, C
1-6Alkyl, C
1-6Alkoxyl group; R
3Be hydrogen, methyl; N=1,2,3.
2. carry out photocuring reaction by unsaturated compound that contains thiazolinyl or the system that contains above-mentioned unsaturated compound, wherein containing at least a compound is compound of Formula I.
Wherein: Z
1=hydrogen, Z; Z is the substituent structure of general formula I I, III, IV.
3. the photocuring of the unsaturated compound by containing thiazolinyl prepares a kind of aqueous polymerization solution or polymeric dispersion in water medium, and wherein containing at least a compound is the compound of Formula I that contains branched hydroxy group.
Wherein: Z
1=hydrogen, Z; Z is the substituent structure of general formula I I, III.
4. the photocuring of the unsaturated compound by containing thiazolinyl prepares a kind of water-soluble polymers or hydrophilic polymer in aqueous media, and wherein containing at least a compound is the compound of Formula I that contains branched hydroxy group.
Wherein: Z
1=hydrogen, Z; Z is the substituent structure of general formula I I, III.
5. according to claim 1, compound of Formula I as light trigger is:
4-(2-hydroxyl-3-acryl oxygen base-propoxy-) benzophenone
4-(2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone
4,4 '-two (2-hydroxyl-3-acryl oxygen base-propoxy-) benzophenone
4,4 '-two (2-hydroxy-3-methyl acryl oxygen base-propoxy-) benzophenone
4-(2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone
4,4 '-two (2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone
4-(2-acryl oxygen base-ethyl) benzophenone
4-(2-methacryloyl oxygen base-ethyl) benzophenone
4,4 '-two (2-acryl oxygen base-ethyl) benzophenone
4,4 '-two (2-methacryloyl oxygen base-ethyl) benzophenone
6. according to claim 1, compound of Formula I is 4-(2-hydroxyl-3-acryl oxygen base-propoxy-) benzophenone and 4 as light trigger, 4 '-two (2-hydroxyl-3-acryl oxygen base-propoxy-) benzophenone.
7. according to claim 1, compound of Formula I is 4-(2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone and 4 as light trigger, 4 '-two (2-hydroxyl-3-allyl group oxygen base-propoxy-) benzophenone.
8. according to claim 1, compound of Formula I is 4-(2-acryl oxygen base-ethyl) benzophenone and 4 as light trigger, 4 '-two (2-acryl oxygen base-ethyl) benzophenone.
9. according to claim 1, compound of Formula I was added to before polyreaction in the polymerization system mixture according to 0.01～20% (relatively all weight ratios of polymerizable thing) as light trigger.
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| CN100427461C (en) * | 2006-03-30 | 2008-10-22 | 上海交通大学 | Polymerisable benzophenone photoinitiator and its preparing method |
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